CN114409504A - Method for preparing 1, 4-butanediol by hydrogenation of 1, 4-butynediol - Google Patents
Method for preparing 1, 4-butanediol by hydrogenation of 1, 4-butynediol Download PDFInfo
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- CN114409504A CN114409504A CN202210045285.5A CN202210045285A CN114409504A CN 114409504 A CN114409504 A CN 114409504A CN 202210045285 A CN202210045285 A CN 202210045285A CN 114409504 A CN114409504 A CN 114409504A
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- butanediol
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 44
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 106
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 239000000047 product Substances 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 21
- UIKQNMXWCYQNCS-UHFFFAOYSA-N 2-hydroxybutanal Chemical compound CCC(O)C=O UIKQNMXWCYQNCS-UHFFFAOYSA-N 0.000 claims abstract description 19
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000376 reactant Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 85
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000011777 magnesium Substances 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 25
- 238000005303 weighing Methods 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- 238000003723 Smelting Methods 0.000 description 12
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- 238000005406 washing Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
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- 230000005611 electricity Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
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- 238000000227 grinding Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- UKDHSAZUXNLNLV-UHFFFAOYSA-N nickel(2+) dinitrate tetrahydrate Chemical compound O.O.O.O.[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O UKDHSAZUXNLNLV-UHFFFAOYSA-N 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- SWSOIFQIPTXLOI-HNQUOIGGSA-N (e)-1,4-dichlorobut-1-ene Chemical compound ClCC\C=C\Cl SWSOIFQIPTXLOI-HNQUOIGGSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 2
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 241000830536 Tripterygium wilfordii Species 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000012805 post-processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention relates to a method for preparing 1, 4-butanediol by hydrogenation of 1, 4-butynediol, wherein a pressurized 1, 4-butynediol aqueous solution enters a low-pressure reactor, a first-step hydrogenation reaction product enters a normal-pressure cyclone separator after being decompressed, reaction liquid is extracted from the top of the separator, and catalyst particles are further removed from the reaction liquid through a bag filter; the reaction liquid enters a pre-separation tower, the reaction liquid is split under a vacuum state, water, n-butyl alcohol and light components are distilled out from the top of the tower, and a mixed water solution containing 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde, acetal and heavy components is discharged from the bottom of the tower; the mixed aqueous solution enters a freezing water heat-removal tubular reactor after being preheated by a pressurization and high-pressure hydrogenation preheater, is converted into 1, 4-butanediol under the action of a catalyst, reactants are extracted from the bottom of the reactor, and a 1, 4-butanediol product is obtained after distillation.
Description
Technical Field
The invention relates to a method for producing 1, 4-butanediol, in particular to a method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol.
Background
1, 4-butanediol (BDO for short) is an important organic and fine chemical raw material, and is widely applied to the fields of medicine, chemical industry, textile, papermaking, automobiles, daily chemical industry and the like. Tetrahydrofuran (THF), polybutylene terephthalate (PBT), gamma-butyrolactone (GBL) and polyurethane resins (PU Resin), paints and plasticizers, etc., as well as brighteners for the solvent and electroplating industries, etc., can be produced from 1, 4-butanediol.
Before world war II, 1, 4-butanediol has been synthesized by Germany using acetylene and formaldehyde as raw materials by the Reppe process. The method solves the danger of acetylene operation under high pressure, and is still the most important production method of 1, 4-butanediol. In the 60 s, Mitsubishi oiling company, Japan, developed a process for preparing 1, 4-butanediol by catalytic hydrogenation of maleic anhydride, and in the 70 s, the company developed a new process for acetoxylation of butadiene. In 1971, the production plant for the chlorination of butadiene was established by the company Tosoh Cauda, Japan. Further, various syntheses using propylene or ethylene as a raw material have been studied successively in the United states and Japan.
The production process of the tripterygium-wilfordii method is not complex and the cost is low. At present, the production capacity of the method is close to 90% of the total capacity of various methods, and the key to the development of the method in future is the supply and price of acetylene raw materials.
The maleic anhydride hydrogenation method, the reaction is carried out in two steps, and tetrahydrofuran is co-produced. The method has high raw material cost, but has less reaction steps, low investment and adjustable obtained co-products, so that research and development are still carried out in many countries.
1, 4-dichlorobutene process, 1, 4-dichlorobutene is an intermediate product in the production of chloroprene from butadiene. The method developed by Toyo Caoda industries is to hydrolyze 1, 4-dichlorobutene with excessive sodium formate at about 110 ℃ to generate 2-butene-1, 4-diol, with the conversion rate close to 100% and the selectivity greater than 90%. After hydrolysis, the free formic acid is neutralized with sodium hydroxide. Then 2-butylene-1, 4-diol is hydrogenated at 100 ℃ and 27MPa in the presence of a nickel-aluminum catalyst to obtain 1, 4-butanediol. The method has the advantages of high public engineering cost and high production cost.
China has abundant coal resources. Compared with other production processes, the raw materials of the Reppe method are mainly supplied for coal post-processing. Therefore, the Reppe method has practical significance in the production of 1, 4-butanediol in China.
The synthesis of 1, 4-butynediol in the first step in the existing production process of the Reppe method is basically consistent, but the use mode of the catalyst is slightly different. The difference of the hydrogenation working section is larger, the first process is that the whole system is subjected to high-pressure fixed bed hydrogenation, and large-flow 1, 4-butynediol aqueous solution with the weight percent of 30-40 is adopted for circulating hydrogenation; the other process is a two-stage method, wherein low-pressure hydrogenation is carried out firstly, and then the addition product is subjected to high-pressure hydrogenation for complete conversion; compared with the two methods, the second method saves the energy consumption of the hydrogenation working section under the condition of ensuring the conversion rate and the product quality;
the traditional two-step hydrogenation process for preparing 1, 4-butanediol comprises the following steps: in the first step (also called as first-stage hydrogenation), a suspension bed (or a bubbling slurry bed) is generally adopted, a Raney-nickel catalyst is used, low-pressure hydrogenation is carried out at 50-80 ℃ and under the hydrogen pressure of 1-3 MPa, 1, 4-butynediol aqueous solution with the concentration of 30-40 wt% is hydrogenated into 1, 4-butanediol aqueous solution, and the solution contains n-butyl alcohol, unsaturated hydrogenation products 1, 4-butylene glycol, 1, 4-butylene glycol isomerization products 4-hydroxybutyraldehyde and acetal and other high-boiling residues and low-boiling residues obtained by condensation reaction of aldehyde and alcohol; because 4-hydroxybutyraldehyde, acetal and 1, 4-butenediol cannot be removed by a rectification method, the purity and quality of products are influenced, and further high-pressure hydrogenation removal is needed; and in the second step (second-stage hydrogenation), the product solution in the first stage is hydrogenated in a fixed bed reactor by using supported nickel as a catalyst at the reaction temperature of 110-160 ℃ and under the hydrogen pressure of 12-21 MPa, and the method mainly relates to the further hydrogenation conversion of a small amount of 1, 4-butylene glycol, an isomerization product, namely hydroxybutyraldehyde and acetal in materials so as to improve the yield of 1, 4-butanediol and reduce the existence of impurities.
The above processes have been disclosed many times in the prior art, but the above processes still adopt a low-concentration and high-flow hydrogenation process in the second-stage hydrogenation process because of the heat removal requirement of the traditional fixed bed trickle reaction system, and a large amount of water (60 wt% -70 wt%) exists in the system, thereby increasing the energy consumption of the system.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol, which achieves the aim of reducing energy consumption by separation in advance.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol comprises the following steps:
step one, feeding a pressurized 30-40 wt% of 1, 4-butynediol aqueous solution into a low-pressure reactor, carrying out a first-step hydrogenation reaction under the action of a Raney nickel-aluminum-X catalyst, feeding a product into a normal-pressure cyclone separator after pressure reduction, separating the Raney nickel-aluminum-X catalyst from the bottom of the separator, collecting a reaction solution from the top, and further removing catalyst particles from the reaction solution through a bag filter;
step two, the reaction liquid enters a pre-separation tower; cutting the reaction liquid under vacuum state, distilling water, n-butanol and light components from the top of the tower, and discharging a mixed aqueous solution containing 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde, acetal and heavy components from the bottom of the tower;
step three, feeding the water, the n-butyl alcohol and the light components separated from the top of the pre-separation tower into a next separation section to extract a byproduct n-butyl alcohol;
and step four, preheating the mixed aqueous solution separated from the bottom of the pre-separation tower through a pressurizing and high-pressure hydrogenation preheater, then feeding the preheated mixed aqueous solution into a chilled water heat-removal tubular reactor, converting 1, 4-butylene glycol, hydroxyl butyraldehyde and acetal into 1, 4-butanediol under the action of a catalyst, extracting reactants from the bottom of the reactor, and distilling to obtain a 1, 4-butanediol product.
Further, in the first step, the Raney nickel-aluminum-X catalyst used in the low-pressure reactor consists of nickel and aluminum in a mass ratio of (0.5-1): 1. the addition amount of X is 1-2 wt% of the total mass of nickel and aluminum, and the metal powder is obtained by treating 25% of NaOH; wherein X is any one of Mg, B, Sr, Cr, S, Ti, La, Sn, W, Mo and Fe. Preferably, X is Mg.
Further, in the step one, the inlet solution of the low-pressure reactor is 30-40 wt% of 1, 4-butynediol aqueous solution, the inlet temperature is 40-45 ℃, the inlet pressure is 1.1-4.1 MPa, and the liquid space velocity is 1-4 h-1(ii) a The inlet gas is 99.99wt% of hydrogen, the inlet pressure is 1.1-4.1 MPa, and the gas space velocity is 11-1.5 h-1(ii) a The liquid outlet pressure is 0.4-0.8 MPa, and the outlet temperature is 60-75 ℃.
Further, the low pressure reactor is a slurry bed reactor with a jacketed heat removal system.
Further, in the second step, the number of theoretical plates of the pre-separation tower is 3-5, and the operating pressure is 15-25 KPa; the operation temperature is 60-75 ℃.
Further, in the fourth step, the high-pressure hydrogenation preheater is a shell-and-tube heat exchanger, the liquid inlet temperature is 60-75 ℃, and the liquid outlet temperature is 95-140 ℃.
Further, in the fourth step, the composition of the catalyst filled in the chilled water heat-removal tubular reactor is as follows: the nickel-based composite material comprises, by weight, 11-22% of nickel, 1-6% of a promoter and the balance of aluminum oxide, wherein the promoter is one of lanthanum, copper and magnesium.
Further, the chilled water heat-removal tubular reactor R is a tubular reactor, a catalyst is filled in the tubular reactor, the shell side is subjected to heat removal by the chilled water, and the reaction temperature is controlled at 95-140 ℃; the reaction pressure is controlled to be 10.0-30.0 MPa, and the liquid airspeed of the reactor is 0.5-2.5 h-1。
Further, the catalyst separated from the bag filter and the catalyst separated from the bottom of the cyclone separator are recycled to the low-pressure reactor to take part in the reaction again.
In the invention, the inventor grasps the reaction rule of low-pressure 1, 4-butynediol hydrogenation and high-pressure pass hydrogenation reaction through a catalyst comparison test, activity evaluation, theoretical calculation and software simulation, screens out a proper catalyst suitable for medium-pressure 1, 4-butynediol hydrogenation and a reasonable reaction form of a high-pressure pass hydrogenation catalyst under high concentration, and achieves the purposes of completing the process target and reducing the energy consumption by separating and changing the form of a hydrogenation reactor in advance for solving the problem of high energy consumption in the conventional two-section 1, 4-butynediol hydrogenation process.
Specifically, compared with the prior art, the invention has the following advantages:
(1) in the prior art, the outlet temperature of the low-pressure reactor material is 60-75 ℃, the material containing about 60 percent of water, butanol and other components needs to be heated to 95-140 ℃ before high-pressure hydrogenation, and a large amount of energy is consumed. According to the invention, under the condition of no heating condition, the solution after low-pressure hydrogenation is separated in advance, and about 60wt% of the weight of the reaction liquid is removed before high-pressure hydrogenation, so that the energy consumption of a high-pressure hydrogenation section is greatly reduced. Meanwhile, the material handling capacity of the high-pressure hydrogenation section is correspondingly reduced, and the size of the whole high-pressure pressurizing equipment is reduced and the investment is greatly reduced when the 1, 4-butanediol handling capacity is the same.
(2) The concentration of high pressure materials and the increase of reactant concentration not only need higher catalyst activity, but also cause the exothermic reaction to be intensified, and higher requirements are put on the heat removal of the reactor. The high-pressure reaction in the prior art adopts common Ni/Al2O3The catalyst has low activity and cannot meet the activity requirement of high-concentration reaction materials. The fixed bed tower reactor has low heat removal efficiency, and can easily cause temperature runaway of a catalyst bed layer to cause irreversible inactivation of the catalyst. On one hand, the newly developed novel efficient hydrogenation catalyst is adopted, the catalyst contains 11-22 wt% of nickel, 1-6 wt% of promoter and the balance of alumina, and the promoter is one of lanthanum, copper and magnesium. The active component nickel of the catalyst is introduced into the carrier by dipping the mixed salt solution, the mixed nickel salt is formed by mixing inorganic nickel salt and organic nickel salt, and the active component can be promoted to be uniformly deposited on the inner surface of the catalyst carrier due to the synergy and competitive adsorption among anions, so that a highly dispersed catalyst product is obtained. Meanwhile, a proper amount of surfactant polyethylene glycol or CTAB is added into the impregnation liquid, on one hand, the effect of increasing the solubility is achieved, on the other hand, the dispersion of nickel species is further promoted, and the carbon deposition generated in the roasting process can also prevent an active componentAgglomeration is separated, and the interaction between the active component and the carrier is adjusted. Due to the adoption of a special catalyst preparation method, the obtained catalyst keeps high dispersion degree under higher active component loading capacity, and the catalyst has proper surface acidity and alkalinity, a proper pore structure and interaction of proper metal and a carrier. Therefore, the catalyst shows high catalytic activity and selectivity in high hydrogenation and has long service life.
(3) Aiming at the problem of aggravation of heat release of high-concentration materials, the traditional high-pressure hydrogenation reactor is optimized, and the original simple fixed bed tower reactor is changed into a high-pressure tube array reactor with better heat removal effect, so that the reaction heat is smoothly removed in the process of high-concentration reaction.
The invention can obtain the 1, 4-butanediol product with the product purity of more than or equal to 99.5 percent and the chroma of less than or equal to 10AHPA through the process flow. The consumption of public works is greatly reduced, the power electricity consumption is lower than 420 kilowatt-hour/ton of 1, 4-butanediol, the steam consumption is lower than 4.5 ton/ton of 1, 4-butanediol, and the circulating cooling water consumption is lower than 320 ton/ton of 1, 4-butanediol.
Drawings
FIG. 1 is a flow diagram of the prior art hydrogenation of 1, 4-butynediol to 1, 4-butanediol.
FIG. 2 is a flow chart of the hydrogenation of 1, 4-butynediol to 1, 4-butanediol according to the present invention.
Detailed Description
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples.
In the following examples, the preparation method of Raney nickel-aluminum-X catalyst can be referred to patent document CN 102744083A. For a method for preparing a catalyst packed in a chilled water heat-removal tubular reactor, reference is made to patent document No. CN 101306368A.
Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
In this example, the raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consisted of: the mass ratio of nickel to aluminum is 0.5: 1, the addition amount of X is 1wt% of the total mass of the nickel and the aluminum, wherein the X is Mg. The preparation process comprises the following steps: respectively weighing 250kg of Ni blocks, 500kg of Al blocks and 7.5kg of Mg, placing the Ni blocks, the 500kg of Al blocks and the 7.5kg of Mg blocks in a medium-large-sized smelting furnace, starting current, after the Ni, the Al and the Mg are molten, carrying out heat preservation smelting at 900 ℃ for 60min, and pouring into water for cooling; grinding the cooled catalyst to 200-mesh powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a NaOH solution with the mass concentration of 25% in batches, uniformly mixing, controlling the temperature to react at 60 ℃ for 30min, washing the mixture for 3 times by using distilled water after the reaction is finished, and washing the mixture to be neutral by using absolute ethyl alcohol.
The chilled water heat-removal tubular reactor R2 is filled with a catalyst composition as follows: 11 wt% of nickel, 1wt% of promoter Mg and the balance of alumina. The catalyst was prepared as follows. Taking the specific surface area as 220 m2·g-1Pore volume of 0.7 cm3·g-188 Kg of alumina carrier with the average pore diameter of 12 nm, 10.6 Kg of magnesium nitrate hexahydrate are taken to prepare 100L of solution, the solution is soaked in the alumina carrier and is kept stand for 30min, and then the alumina carrier is dried at 120 ℃ for 12 h and roasted at 500 ℃ for 6 h to obtain the carrier containing the promoter Mg. Vacuumizing the carrier at 150 deg.C for 10 min, and cooling to room temperature. Weighing 29.7 Kg of nickel nitrate hexahydrate, 21.3 Kg of nickel nitrate tetrahydrate and 2 Kg of polyethylene glycol to prepare 100L of solution, dipping the solution on the carrier containing the promoter Mg, standing for 20 min, and filtering out the rest solution; drying at 80 deg.C for 10 h, calcining at 250 deg.C for 10 h, introducing hydrogen gas, reducing at 450 deg.C for 5h, and deactivating with oxygen.
(1) Pressurizing to 4.1MPa, introducing 30wt% of 1, 4-butynediol aqueous solution at 40 ℃ into a low-pressure reactor R1, keeping the reaction pressure at 4.1MPa, the reaction temperature at 60 ℃, and adjusting the space velocity of the reaction liquid to 1h-1The pressure of the added hydrogen (99.99%) is 4.1MPa, and the gas space velocity is 1.5h-1Carrying out the first hydrogenation step; the product is decompressed to 0.4MPa and enters cycloneA separator S1; raney nickel-aluminum-X catalyst separated from the bottom of the cyclone separator S1, reaction liquid is extracted from the top, and the reaction liquid is further removed with catalyst particles through a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone separator S1 are recycled to the low-pressure reactor R1 to take part in the reaction again;
(2) the reaction solution thus treated was introduced into a preseparator T1, the number of theoretical plates being 5, and the operating temperature was maintained at 75 ℃ at 15 KPa. Cutting the reaction liquid, distilling out water, butanol and light components from the top of the tower, and discharging a mixed aqueous solution of 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde, acetal and heavy components from the bottom of the tower;
(3) water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract a byproduct butanol;
(4) preheating the mixed aqueous solution separated from the bottom of a pre-separation tower T1 by a pressurizing and high-pressure hydrogenation preheater E1, heating to 120 ℃, boosting the pressure to 20MPa, and allowing the mixed aqueous solution to enter a chilled water heat-removal tubular reactor R2 from the top in a trickle manner, wherein the reaction temperature is controlled at 140 ℃; the reaction pressure is controlled at 20MPa, and the space velocity is 0.5h-1(ii) a Further converting small amounts of 1, 4-butenediol, hydroxybutyraldehyde and acetal to 1, 4-butanediol, the reactant was withdrawn from the bottom of reactor R2. Distilling to obtain 1, 4-butanediol product with purity of 99.6% and chroma equal to 5 AHPA. 400 kilowatt-hour/ton of 1, 4-butanediol is consumed by power electricity, 4.1 ton/ton of 1, 4-butanediol is consumed by steam, and 300 ton/ton of 1, 4-butanediol is consumed by circulating cooling water.
Comparative example 1
In this example, the same raney nickel-aluminum-X catalyst as in example 1 was used in a low pressure reactor, and a high pressure hydrogenation catalyst containing 11 wt% nickel, 1wt% promoter Mg, and the balance alumina. The prior hydrogenation process is adopted:
(1) pressurizing to 4.1MPa, introducing a 30wt% 1, 4-butynediol aqueous solution at 40 ℃ into a low-pressure hydrogenation reactor, keeping the reaction pressure at 4.1MPa, keeping the reaction temperature at 60 ℃, and adjusting the space velocity of the reaction liquid to 1h-1The pressure of hydrogen (99.99%) is 4.1MPa, and the gas space velocity is 1.5 h-1Carrying out the first hydrogenation step; the product is decompressed to 0.4MPa and enters a separator, and the separated catalyst is circulated to the low-pressure reactor to take part in the reaction again;
(2) preheating the separated material by a pressurizing and high-pressure hydrogenation preheater, heating to 120 ℃, boosting to 20MPa, and allowing the material to enter a fixed bed reactor from the top in a trickle mode, wherein the reaction temperature is controlled at 140 ℃; the reaction pressure is controlled at 20MPa, and the space velocity is 0.5h-1(ii) a Further converting small amounts of 1, 4-butenediol, hydroxybutyraldehyde and acetal to 1, 4-butanediol, and withdrawing the reactants from the bottom of the reactor. Distilling to obtain 1, 4-butanediol product with purity of 99.5% and chroma equal to 5 AHPA. 485 kilowatt-hour/ton of 1, 4-butanediol is consumed by power electricity, 5.3 ton/ton of 1, 4-butanediol is consumed by steam, and 353 ton/ton of 1, 4-butanediol is consumed by circulating cooling water.
Example 2
In this example, the raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consisted of: the mass ratio of nickel to aluminum is 0.6: 1, the addition amount of X is 1wt% of the total mass of the nickel and the aluminum, wherein the X is Mg. The preparation process comprises the following steps: respectively weighing 300kg of Ni blocks, 500kg of Al blocks and 8kg of Mg, placing the Ni blocks, the Al blocks and the Mg blocks in a medium-large-sized smelting furnace, starting current, after the Ni, the Al and the Mg are molten, carrying out heat preservation smelting at 900 ℃ for 60min, and pouring the molten Ni, the Al and the Mg blocks into water for cooling; grinding the cooled catalyst to 200-mesh powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a NaOH solution with the mass concentration of 25% in batches, uniformly mixing, controlling the temperature to react at 60 ℃ for 30min, washing the mixture for 3 times by using distilled water after the reaction is finished, and washing the mixture to be neutral by using absolute ethyl alcohol.
The chilled water heat-removal tubular reactor R2 is filled with a catalyst composition as follows: 13 wt% of nickel, 3 wt% of promoter La and the balance of alumina. The catalyst is prepared by the following steps: taking the specific surface area as 300 m2·g-1Pore volume of 1.1 cm3·g-184 Kg of alumina carrier with the average pore diameter of 17 nm, taking 9.4 Kg of lanthanum nitrate hexahydrate to prepare 120L of solution, dipping the solution into the alumina carrier, standing for 20 min, drying at 110 ℃ for 10 h, and roasting at 400 ℃ for 6 h to obtain the catalyst La-containing aluminaAnd (3) a carrier. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for later use. Weighing 39.6 Kg of nickel nitrate hexahydrate, 17.0 Kg of nickel nitrate tetrahydrate and 3Kg of CTAB to prepare 120L of solution, impregnating the solution on the carrier containing the promoter La, standing for 30min, and filtering out the rest solution; drying at 100 deg.C for 8 hr, calcining at 450 deg.C for 6 hr, introducing hydrogen gas, reducing at 400 deg.C for 5 hr, and protecting the reduced catalyst with liquid.
(1) Pressurizing to 3.0MPa, introducing a 35wt% 1, 4-butynediol aqueous solution at 40 ℃ into a low-pressure reactor R1, keeping the reaction pressure at 3.0MPa, the reaction temperature at 60 ℃, and adjusting the space velocity of the reaction liquid to 2h-1The pressure of hydrogen (99.99%) is 3MPa, and the gas space velocity is 3h-1Carrying out the first hydrogenation step; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney nickel-aluminum-X catalyst is separated from the bottom of the cyclone separator S1, the reaction liquid is extracted from the top, and the catalyst particles are further removed from the reaction liquid through a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone separator S1 are recycled to the low-pressure reactor R1 to take part in the reaction again;
(2) the reaction liquid treated by the above enters a pre-separation tower T1, and the number of theoretical plates is 4; at 20KPa, the operating temperature was maintained at 70 ℃. The reaction liquid is cut, water, butanol and light components are distilled from the top of the tower, and the aqueous solution of heavy components, 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde and acetal comes out from the bottom of the tower;
(3) water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract a byproduct butanol;
(4) preheating the solution separated from the bottom of a pre-separation tower T1 by a pressurizing and high-pressure hydrogenation preheater E1, heating to 120 ℃, boosting the pressure to 25MPa, and allowing the solution to enter a chilled water heat-removal tubular reactor R2 from the top in a trickle manner, wherein the reaction temperature is controlled at 130 ℃; the reaction pressure is controlled at 25MPa, and the space velocity is 1.0h-1(ii) a Further converting small amounts of 1, 4-butenediol, hydroxybutyraldehyde and acetal to 1, 4-butanediol, the reactant was withdrawn from the bottom of reactor R2. Distilling to obtain 1, 4-butanediol product with purity of 99.7% and chroma equal to 3 AHPA.400 kilowatt-hour/ton of 1, 4-butanediol is consumed by power electricity, 4.1 ton/ton of 1, 4-butanediol is consumed by steam, and 300 ton/ton of 1, 4-butanediol is consumed by circulating cooling water.
Example 3
In this example, the raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consisted of: the mass ratio of nickel to aluminum is 0.7: 1, the addition amount of X is 1wt% of the total mass of the nickel and the aluminum, wherein the X is Mg. The preparation process comprises the following steps: respectively weighing 350kg of Ni blocks, 500kg of Al blocks and 8.5kg of Mg, placing the Ni blocks, the 500kg of Al blocks and the 8.5kg of Mg in a medium-large-sized smelting furnace, starting current, after the Ni, the Al and the Mg are molten, carrying out heat preservation smelting at 900 ℃ for 60min, and pouring into water for cooling; grinding the cooled catalyst to 200-mesh powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a NaOH solution with the mass concentration of 25% in batches, uniformly mixing, controlling the temperature to react at 60 ℃ for 30min, washing the mixture for 3 times by using distilled water after the reaction is finished, and washing the mixture to be neutral by using absolute ethyl alcohol;
the chilled water heat-removal tubular reactor R2 is filled with a catalyst composition as follows: 19 wt% of nickel, 5wt% of promoter Cu and the balance of alumina. The catalyst is prepared by the following steps: taking the specific surface area as 150 m2·g-1Pore volume of 1.3 cm3·g-176 Kg of alumina carrier with the average pore diameter of 20 nm, 19.0 Kg of copper nitrate trihydrate are taken to prepare 100L of solution, the solution is soaked in the alumina carrier and is kept stand for 30min, and then the alumina carrier is dried for 10 h at 110 ℃ and roasted for 6 h at 400 ℃ to obtain the carrier containing the promoter Cu. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for later use. Weighing 49.5 Kg of nickel nitrate hexahydrate, 38.1 Kg of nickel nitrate tetrahydrate and 2 Kg of CTAB to prepare 130L of solution, impregnating the solution on the carrier containing the promoter Cu, standing for 30min, and filtering out the rest solution; drying at 100 deg.C for 8 hr, calcining at 450 deg.C for 6 hr, introducing hydrogen gas, reducing at 400 deg.C for 5 hr, and protecting the reduced catalyst with liquid.
(1) Pressurizing to 2.5MPa, introducing a 35wt% 1, 4-butynediol aqueous solution at 40 ℃ into a low-pressure reactor R1, keeping the reaction pressure at 2.5MPa, the reaction temperature at 60 ℃, and adjusting the space velocity of the reaction liquid to 3h-1Adding hydrogen gas(99.99%) pressure of 2.5MPa, gas space velocity of 4h-1Carrying out the first hydrogenation step; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney-nickel catalyst separated from the bottom of the cyclone separator S1 is extracted from the top of the cyclone separator S1, and the reaction liquid is used for further removing catalyst particles through a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone separator S1 are recycled to the low-pressure reactor R1 to take part in the reaction again;
(2) the reaction liquid treated by the above enters a pre-separation tower T1, and the number of theoretical plates is 4; at 20KPa, the operating temperature was maintained at 70 ℃. The reaction liquid is cut, water, butanol and light components are distilled from the top of the tower, and the aqueous solution of heavy components, 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde and acetal comes out from the bottom of the tower;
(3) water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract a byproduct butanol;
(4) preheating the solution separated from the bottom of a pre-separation tower T1 by a pressurizing and high-pressure hydrogenation preheater E1, heating to 110 ℃, boosting the pressure to 25MPa, and allowing the solution to enter a chilled water heat-removal tubular reactor R2 from the top in a trickle manner, wherein the reaction temperature is controlled at 120 ℃; the reaction pressure is controlled at 25MPa, and the space velocity is 1.5h-1(ii) a Further converting small amounts of 1, 4-butenediol, hydroxybutyraldehyde and acetal to 1, 4-butanediol, and withdrawing the reactants from the bottom of the reactor. Distilling to obtain 1, 4-butanediol product with purity of 99.6% and chroma equal to 3 AHPA. 395 Kwhr/ton of 1, 4-butanediol is consumed by power electricity, 4.0 ton/ton of 1, 4-butanediol is consumed by steam, and 295 ton/ton of 1, 4-butanediol is consumed by circulating cooling water.
Example 4
In this example, the raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consisted of: the mass ratio of nickel to aluminum is 0.8: 1, the addition amount of X is 1wt% of the total mass of the nickel and the aluminum, wherein the X is Mg. The preparation process comprises the following steps: respectively weighing 400kg of Ni blocks, 500kg of Al blocks and 9kg of Mg, placing the Ni blocks, the Al blocks and the Mg blocks in a medium-large-sized smelting furnace, starting current, after the Ni, the Al and the Mg are molten, carrying out heat preservation smelting at 900 ℃ for 60min, and pouring the molten Ni, the Al and the Mg blocks into water for cooling; grinding the cooled catalyst to 200-mesh powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a NaOH solution with the mass concentration of 25% in batches, uniformly mixing, controlling the temperature to react at 60 ℃ for 30min, washing the mixture for 3 times by using distilled water after the reaction is finished, and washing the mixture to be neutral by using absolute ethyl alcohol;
the chilled water heat-removal tubular reactor R2 is filled with a catalyst composition as follows: the nickel content is 22 wt%, the promoter Cu content is 6 wt%, and the balance is alumina. The catalyst is prepared by the following steps: taking the specific surface area as 150 m2·g-1Pore volume of 1.3 cm3·g-172 Kg of alumina carrier with the average pore diameter of 20 nm, 22.8 Kg of copper nitrate trihydrate are taken to prepare 100L of solution, the solution is soaked in the alumina carrier and stands for 30min, then the alumina carrier is dried for 10 h at 110 ℃, and roasted for 6 h at 400 ℃ to obtain the carrier containing the promoter Cu. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for later use. Weighing 74.3 Kg of nickel nitrate hexahydrate, 29.7 Kg of nickel nitrate tetrahydrate and 2 Kg of CTAB to prepare 130L of solution, impregnating the solution on the carrier containing the promoter Cu, standing for 30min, and filtering out the rest solution; drying at 100 deg.C for 8 hr, calcining at 450 deg.C for 6 hr, introducing hydrogen gas, reducing at 400 deg.C for 5 hr, and protecting the reduced catalyst with liquid.
(1) Pressurizing to 2.0MPa, introducing 40wt% of 1, 4-butynediol aqueous solution at 40 ℃ into a low-pressure reactor R1, keeping the reaction pressure at 2.0MPa, the reaction temperature at 60 ℃, and adjusting the space velocity of the reaction liquid to 4h-1The pressure of hydrogen (99.99%) is 2.0MPa, and the gas space velocity is 2h-1Carrying out the first hydrogenation step; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney-nickel catalyst separated from the bottom of the cyclone separator S1 is extracted from the top of the cyclone separator S1, and the reaction liquid is used for further removing catalyst particles through a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone separator S1 are recycled to the low-pressure reactor R1 to take part in the reaction again;
(2) the reaction liquid treated by the above enters a pre-separation tower T1, and the number of theoretical plates is 5; at 15KPa, the operating temperature was maintained at 75 ℃. The reaction liquid is cut, water, butanol and light components are distilled from the top of the tower, and the aqueous solution of heavy components, 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde and acetal comes out from the bottom of the tower;
(3) water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract a byproduct butanol;
(4) preheating the solution separated from the bottom of a pre-separation tower T1 by a pressurizing and high-pressure hydrogenation preheater E1, heating to 120 ℃, boosting the pressure to 25MPa, and allowing the solution to enter a chilled water heat-removal tubular reactor R2 from the top in a trickle manner, wherein the reaction temperature is controlled at 130 ℃; the reaction pressure is controlled at 25MPa, and the space velocity is 1.5h-1(ii) a Further converting small amount of 1, 4-butylene glycol, hydroxy butyraldehyde and acetal into 1, 4-butylene glycol, and taking out reactant from the bottom R2 of the reactor. Distilling to obtain 1, 4-butanediol product with purity of 99.7% and chroma equal to 2 AHPA. 400 kilowatt-hour/ton of 1, 4-butanediol is consumed by power electricity, 4.1 ton/ton of 1, 4-butanediol is consumed by steam, and 300 ton/ton of 1, 4-butanediol is consumed by circulating cooling water.
Example 5
In this example, the raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consisted of: the mass ratio of nickel to aluminum is 1: 1, the addition amount of X is 2wt% of the total mass of the nickel and the aluminum, wherein the X is Mg. The preparation process comprises the following steps: respectively weighing 400kg of Ni blocks, 500kg of Al blocks and 9kg of Mg, placing the Ni blocks, the Al blocks and the Mg blocks in a medium-large-sized smelting furnace, starting current, after the Ni, the Al and the Mg are molten, carrying out heat preservation smelting at 900 ℃ for 60min, and pouring the molten Ni, the Al and the Mg blocks into water for cooling; grinding the cooled catalyst to 200-mesh powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a NaOH solution with the mass concentration of 25% in batches, uniformly mixing, controlling the temperature to react at 60 ℃ for 30min, washing the mixture for 3 times by using distilled water after the reaction is finished, and washing the mixture to be neutral by using absolute ethyl alcohol;
the chilled water heat-removal tubular reactor R2 is filled with a catalyst composition as follows: the nickel content is 22 wt%, the promoter Cu content is 6 wt%, and the balance is alumina. The catalyst is prepared by the following steps: taking the specific surface area as 150 m2·g-1Pore volume of 1.3 cm3·g-172 Kg of alumina carrier with an average pore diameter of 20 nm, and 22.8 Kg of copper nitrate trihydrate were prepared into 100L of solutionAnd soaking the solution into an alumina carrier, standing for 30min, drying at 110 ℃ for 10 h, and roasting at 400 ℃ for 6 h to obtain the carrier containing the promoter Cu. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for later use. Weighing 74.3 Kg of nickel nitrate hexahydrate, 29.7 Kg of nickel nitrate tetrahydrate and 2 Kg of CTAB to prepare 130L of solution, impregnating the solution on the carrier containing the promoter Cu, standing for 30min, and filtering out the rest solution; drying at 100 deg.C for 8 hr, calcining at 450 deg.C for 6 hr, introducing hydrogen gas, reducing at 400 deg.C for 5 hr, and protecting the reduced catalyst with liquid.
(1) Pressurizing to 1.1MPa, introducing 40wt% of 1, 4-butynediol aqueous solution at 45 ℃ into a low-pressure reactor R1, keeping the reaction pressure at 1.1MPa, the reaction temperature at 75 ℃, and adjusting the space velocity of the reaction liquid to 4h-1The pressure of the added hydrogen (99.99%) is 1.1MPa, and the gas space velocity is 1.5h-1Carrying out the first hydrogenation step; the product is decompressed to 0.8MPa and enters a cyclone separator S1; the Raney-nickel catalyst separated from the bottom of the cyclone separator S1 is extracted from the top of the cyclone separator S1, and the reaction liquid is used for further removing catalyst particles through a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone separator S1 are recycled to the low-pressure reactor R1 to take part in the reaction again;
(2) the reaction liquid treated by the above enters a pre-separation tower T1, and the number of theoretical plates is 3; at 25KPa, the operating temperature was maintained at 60 ℃. The reaction liquid is cut, water, butanol and light components are distilled from the top of the tower, and the aqueous solution of heavy components, 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde and acetal comes out from the bottom of the tower;
(3) water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract a byproduct butanol;
(4) preheating the solution separated from the bottom of a pre-separation tower T1 by a pressurizing and high-pressure hydrogenation preheater E1, heating to 95 ℃, boosting the pressure to 10MPa, and allowing the solution to enter a chilled water heat-removal tubular reactor R2 from the top in a trickle manner, wherein the reaction temperature is controlled at 95 ℃; the reaction pressure is controlled at 10MPa, and the space velocity is 2.5h-1(ii) a Further converting small amounts of 1, 4-butenediol, hydroxybutyraldehyde and acetal to 1, 4-butaneDiol, reactant is taken out from the bottom of the reactor at the part R2. Distilling to obtain 1, 4-butanediol product with purity of 99.7% and chroma equal to 2 AHPA. 380 kilowatt-hour/ton of 1, 4-butanediol is consumed by power electricity, 3.8 ton/ton of 1, 4-butanediol is consumed by steam, and 290 ton/ton of 1, 4-butanediol is consumed by circulating cooling water.
Example 6
In this example, the raney nickel-aluminum-X catalyst used in the low pressure reactor R1 consisted of: the mass ratio of nickel to aluminum is 0.8: 1, the addition amount of X is 1wt% of the total mass of the nickel and the aluminum, wherein the X is Mg. The preparation process comprises the following steps: respectively weighing 400kg of Ni blocks, 500kg of Al blocks and 9kg of Mg, placing the Ni blocks, the Al blocks and the Mg blocks in a medium-large-sized smelting furnace, starting current, after the Ni, the Al and the Mg are molten, carrying out heat preservation smelting at 900 ℃ for 60min, and pouring the molten Ni, the Al and the Mg blocks into water for cooling; grinding the cooled catalyst to 200-mesh powder; weighing a proper amount of catalyst powder in batches, adding the catalyst powder into a NaOH solution with the mass concentration of 25% in batches, uniformly mixing, controlling the temperature to react at 60 ℃ for 30min, washing the mixture for 3 times by using distilled water after the reaction is finished, and washing the mixture to be neutral by using absolute ethyl alcohol;
the chilled water heat-removal tubular reactor R2 is filled with a catalyst composition as follows: the nickel content is 22 wt%, the promoter Cu content is 6 wt%, and the balance is alumina. The catalyst is prepared by the following steps: taking the specific surface area as 150 m2·g-1Pore volume of 1.3 cm3·g-172 Kg of alumina carrier with the average pore diameter of 20 nm, 22.8 Kg of copper nitrate trihydrate are taken to prepare 100L of solution, the solution is soaked in the alumina carrier and stands for 30min, then the alumina carrier is dried for 10 h at 110 ℃, and roasted for 6 h at 400 ℃ to obtain the carrier containing the promoter Cu. Drying the carrier at 150 ℃ for 10 h, and cooling to room temperature for later use. Weighing 74.3 Kg of nickel nitrate hexahydrate, 29.7 Kg of nickel nitrate tetrahydrate and 2 Kg of CTAB to prepare 130L of solution, impregnating the solution on the carrier containing the promoter Cu, standing for 30min, and filtering out the rest solution; drying at 100 deg.C for 8 hr, calcining at 450 deg.C for 6 hr, introducing hydrogen gas, reducing at 400 deg.C for 5 hr, and protecting the reduced catalyst with liquid.
(1) The 1, 4-butynediol aqueous solution which is pressurized to 2.0MPa and 40wt% at 40 ℃ enters a low-pressure reactorR1, keeping the reaction pressure at 2.0MPa, keeping the reaction temperature at 60 ℃, and adjusting the space velocity of the reaction liquid to 4h-1The pressure of the added hydrogen (99.99%) is 2.0MPa, and the gas space velocity is 11 h-1Carrying out the first hydrogenation step; the product is decompressed to 0.4MPa and enters a cyclone separator S1; the Raney-nickel catalyst separated from the bottom of the cyclone separator S1 is extracted from the top of the cyclone separator S1, and the reaction liquid is used for further removing catalyst particles through a bag filter S2; the catalyst separated from the bag filter S2 and the catalyst separated from the bottom of the cyclone separator S1 are recycled to the low-pressure reactor R1 to take part in the reaction again;
(2) the reaction liquid treated by the above enters a pre-separation tower T1, and the number of theoretical plates is 5; at 15KPa, the operating temperature was maintained at 75 ℃. The reaction liquid is cut, water, butanol and light components are distilled from the top of the tower, and the aqueous solution of heavy components, 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde and acetal comes out from the bottom of the tower;
(3) water, butanol and light components separated from the top of the pre-separation tower T1 enter the next separation section to extract a byproduct butanol;
(4) preheating the solution separated from the bottom of a pre-separation tower T1 by a pressurizing and high-pressure hydrogenation preheater E1, heating to 140 ℃, boosting the pressure to 30MPa, and allowing the solution to enter a chilled water heat-removal tubular reactor R2 from the top in a trickle manner, wherein the reaction temperature is controlled at 140 ℃; the reaction pressure is controlled at 30MPa, and the space velocity is 0.5h-1(ii) a Further converting small amount of 1, 4-butylene glycol, hydroxy butyraldehyde and acetal into 1, 4-butylene glycol, and taking out reactant from the bottom R2 of the reactor. Distilling to obtain 1, 4-butanediol product with purity of 99.7% and chroma equal to 2 AHPA. The power electricity consumes 420 kilowatt-hour/ton of 1, 4-butanediol, the steam consumes 4.5 ton/ton of 1, 4-butanediol, and the circulating cooling water consumes 320 ton/ton of 1, 4-butanediol.
Claims (9)
1. A method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol is characterized by comprising the following steps:
step one, feeding a pressurized 30-40 wt% of 1, 4-butynediol aqueous solution into a low-pressure reactor, carrying out a first-step hydrogenation reaction under the action of a Raney nickel-aluminum-X catalyst, feeding a product into a normal-pressure cyclone separator after pressure reduction, separating the Raney nickel-aluminum-X catalyst from the bottom of the separator, collecting a reaction solution from the top, and further removing catalyst particles from the reaction solution through a bag filter;
step two, the reaction liquid enters a pre-separation tower; cutting the reaction liquid under vacuum state, distilling water, n-butanol and light components from the top of the tower, and discharging a mixed aqueous solution containing 1, 4-butanediol, 1, 4-butenediol, hydroxybutyraldehyde, acetal and heavy components from the bottom of the tower;
step three, feeding the water, the n-butyl alcohol and the light components separated from the top of the pre-separation tower into a next separation section to extract a byproduct n-butyl alcohol;
and step four, preheating the mixed aqueous solution separated from the bottom of the pre-separation tower through a pressurizing and high-pressure hydrogenation preheater, then feeding the preheated mixed aqueous solution into a chilled water heat-removal tubular reactor, converting 1, 4-butylene glycol, hydroxyl butyraldehyde and acetal into 1, 4-butanediol under the action of a catalyst, extracting reactants from the bottom of the reactor, and distilling to obtain a 1, 4-butanediol product.
2. The method for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol according to claim 1, wherein: in the first step, the Raney nickel-aluminum-X catalyst used in the low-pressure reactor consists of nickel and aluminum in a mass ratio of (0.5-1): 1. the addition amount of X is 1-2 wt% of the total mass of nickel and aluminum, and the metal powder is obtained by treating 25% of NaOH; wherein X is any one of Mg, B, Sr, Cr, S, Ti, La, Sn, W, Mo and Fe.
3. The process for the hydrogenation of 1, 4-butynediol to 1, 4-butanediol of claim 1 or 2, wherein: in the first step, the inlet solution of the low-pressure reactor is 30-40 wt% of 1, 4-butynediol aqueous solution, the inlet temperature is 40-45 ℃, the inlet pressure is 1.1-4.1 MPa, and the liquid space velocity is 1-4 h-1(ii) a The inlet gas is 99.99wt% of hydrogen, the inlet pressure is 1.1-4.1 MPa, and the gas space velocity is 11-1.5 h-1(ii) a The liquid outlet pressure is 0.4-0.8 MPa, and the outlet temperature is 60-75 ℃.
4. The process of claim 3 for the hydrogenation of butynediol 1,4 to butanediol, wherein: the low pressure reactor is a slurry bed reactor with a jacketed heat removal system.
5. The process of hydrogenation of butynediol 1,4 to butanediol of claim 1, 2 or 4, wherein: in the second step, the number of theoretical plates of the pre-separation tower is 3-5, and the operating pressure is 15-25 KPa; the operation temperature is 60-75 ℃.
6. The process of claim 5 for the hydrogenation of butynediol 1,4 to butanediol, wherein: in the fourth step, the high-pressure hydrogenation preheater is a shell-and-tube heat exchanger, the liquid inlet temperature is 60-75 ℃, and the liquid outlet temperature is 95-140 ℃.
7. The process of claim 1 or 6 for the hydrogenation of butynediol-1, 4 to butanediol, wherein: in the fourth step, the composition of the catalyst filled in the chilled water heat-removal tubular reactor is as follows: the nickel-based composite material comprises, by weight, 11-22% of nickel, 1-6% of a promoter and the balance of aluminum oxide, wherein the promoter is one of lanthanum, copper and magnesium.
8. The process of claim 7 for the hydrogenation of butynediol 1,4 to butanediol, wherein: the chilled water heat-removal tubular reactor R is a tubular reactor, a catalyst is filled in the tubular reactor, the shell side is subjected to heat removal by chilled water, and the reaction temperature is controlled to be 95-140 ℃; the reaction pressure is controlled to be 10.0-30.0 MPa, and the liquid airspeed of the reactor is 0.5-2.5 h-1。
9. The process of claim 1 or 8 for the hydrogenation of butynediol-1, 4 to butanediol, wherein: the catalyst separated from the bag filter and the catalyst separated from the bottom of the cyclone separator are circulated to the low-pressure reactor to take part in the reaction again.
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